Copper-containing azo dyestuffs



Patented May 12, 1953 2,638,468 COPPER-CONTAINING AZO DYESTUFFS WalterWehrli, Basel, Switzerland, assignor to Sandoz Limited, Basel,Switzerland, a Swiss No Drawing. Application January 16, 1951, Se-

rial No. 206,311. In Switzerland August 24,

6 Claims.

1 The present application is a continuation-inpart application of mycopending application Ser. No. 604,727, filed on July 12, 1945 (nowabandoned).

l-hydroxynaphthalene-B 8-disulfonic acid, 2-hydroxynaphthalene-36-disulfonic acid, Z-hydroXynaphthalene-G B-disulfonic acid, 1 hydroxy 8chloro naphthalene 3:6 di- The present invention relates to copper con-5 sulfonic acid, taining azo dyestuffs dyeing cellulosic fibers in 1hydroxy 8 methoxynaphthalene 3:6 divivid blue to navy blue shades ofgood fastness sulfonic acid, properties. 1-hydroxynaphthalene-3 6S-trisulfonic acid,

It has been found that valuable copperconl-hydroxynaphthalene-Sz5z7-trisulfonic acid, tainingazo dyestuffs canbe obtained in trisazo 10 l:8-disydroxynaphthalene-3zfi-disulfonic acid,dyestuffs of the formula 2-amino-5-hydroxynaphthalene-'Z-sulfonic acid,

N-aryl in which A stands for the radical of a compound 2 acetylamino 5hydroxynaphthalene 7- of the naphthalene series having a, hydroxy groupsulfonic acid, in ortho-position to the azo bridge, R stands for 2benzoylamino 5 hydroxynaphthalene 7- a member selected from the groupconsisting of sulfonic acid, hydrogen, lower alkyl and a mononuclearradical 2 phenylamino 5 hydroxynaphthalene 7- of the benzene series,aryl stands for a radical sulfonic acid, selected'froin the groupconsisting of the benzene 2-amino-8-hydroxynaphthalene-6-sulionic acid,and naphthalene series and wherein n is one of 2 acetylamino 8hydroxynaphthalene 6- the integers one to three, are treated withcopsulfonic acid, per-yielding substances. 1 amino 8 hydroxynaphthalene3:6 di- The productionof the trisazo dyestufis takes sulfonic acid,place in the conventional manner and needs no 1 acetylamino 8hydroxynaphthalene 3:6- further explanation. U disulfonic acid,

The conversion into the complex copper com- 1 amino 8 hydroxynaphthalene2:4 dipounds may be effected according to various sulfonic acid, methodsknown from the litera ur for instance '1 acetylamino 8hydroxynaphthalene 2:4- by heating in a slightly alkaline aqueous mediumdisulfonic acid, with copper oxide-ammonia complex in the pres- 2 amino8 hydroxynaphthalene 3:6 dience or absence of organic bases or in the mesulfonic acid, of alkaline metal salts of aliphatic monocar- 40 2acetylamino 8 hydroxynaphthalene 3:6- boxylic acids with copper salts.The coppering disulfonic id, can be rega e as fi s when e tW0 eth- 1acetylamino 8 hydroxynaphthalen 4- oxy groups derived from the4:4-diamino-3:3'- sulfonic d, dimethoxydiphenyl are split ofi.

The following data serve for a better illus- Aryl can, for example, bederi d from t tration of the invention, no restriction of its scopefollowing amines of the benzene or naphthalene being intended. series;

Instead of A the following compounds may for I instance be used: f i

5Q l-ammobenzene -2- or -3- or -4-sulfonic acid,1-hydroxynaphthalene-4-sulfonic acid, 1-amino-2- or -3- or-4-chlorobenzene, 2-hydroxynaphthalene-6-sulfonic acid, l-amino-2- or-3- or -4-methylbenzene, 2-hydroxynaphtha1ene-4-sulfonic acid,1-amin0-2z4- or -2:5 or-zzfi-dimethylbenzene,2-hydroxynaphthalene-7-sulfonic acid, 1-amino-2- or +3- or-4-n1ethoxybenzene, l-hydroxynaphthalene-3:fi-disulfonic acid,l-naphthylamine,

3 4 z-naphthylamine, dried. It is soluble in water with a blue colora-1-naphthylamine-4-sulfonic acid, tion and in concentrated sulfuric acidwith a 1-naphthylamine-6-su1fonic acid, bluish green coloration and dyescotton and rel-naphthylamine-'7-sulfonic acid, generated cellulose inclear blue shades, possessing Z-naphthylamine-l-sulfonic acid, 5 verygood fastness to light, to washing and to 2-naphthy1arnine-6-sulfonicacid, water. 1 -naphthylamine-3 a fi-disulfonic acid, Example 21-naphtliylamine- 3z8disulfonie acid,- 111 1 parts of the :sodmmsalt ofthe trisazo dye- 1-naphthylam1ne-4 8-d1sulfonic acid, stufi of theformula HQzS c gH H100 ooH, OH

1E HO ,8 -NH2 if NGOOH:

2-naphthylamine-3:fi-disulfonic acid, are dissolved in 2000 parts ofWater with addition 2-naphthylamine-4:8-disu1fonic acid, 20 of 20 partsof sodium carbonate. To this solu- 2-naphthylamine-5:7-disulfonicacid,tion there are added, by portions, andwhile stir- 2-naphthy-laminefizs-disulfonicaoid. ring at 80-90? C., 500 parts of'anaqueous $0111?-The following radicals may; for instance,-stand won ining 50 parts ofrys allis d copper forR: 0 sulfate and 85 parts of a concentratedaqueous -Methsl ammoniasolution. The mixture isstirredifor 5 Ethyl,hours-at 80-90 C., heated within 1 hour to boiling -Pherwl, andboiledfor hours under reflux Theu-com- -2- or 3-or.4=,-methoxyphenyl,; 9copper pound thus obtained is salted out, or+3For4mh10mphenylr filteredanddried. It is, soluble in water with a 2 o g 4am thylph ylbluecoloration and iii-concentrated sulfuric acid- 3acarboxya4hydmxyphgnyllV w1th a bluish green coloration, anddye cotton 3 or 4 sufo henyl and regenerated cellulose in blue shades, pos- 3 or 4carboxyphenyl sessing very" good fastness to, light, to washing Thefollowing examples illustrate how the inand) Watervention may be carriedout in practice, but the 3 ea mples ar in no way l tat v he parts are115,7 parts of the sodium salt of the trisazo dyeglven by Welghtstufi'ofthe formula (1)1! :0? can; no

Bids 3 i w Osoln Example 1 are added with-vigorous stirring at 80-90" C.to 97.9 parts cfthe sodium saltoi thetrisazoldyethemeltof 100 P r ofWater; 5Parts0fcrystab tufi of the fo mula line copper sulfate.v and350. parts, of, crystalline.

OQH:

HOsS

are dissolved in 2000 parts of Water under addisodium acetate. Themelt:is stirrediforqrhours tion of 20 parts of du m onat o t is attic-90s c.,brought toboiling within 2 hours u ni r e ge s r ii s iei m and boiledforfurtherldhoursiundenrefluxz, The perature of 80-90 C. and whilestirring 500 parts 1 o V of an aqueous solution containing 50 parts offi t 15 g i g wo'parts'ojwater crystallised copper sulfate and 85 partsoflai (50119- rPppe m eremm an the Wholly m f andcentr-ate'diaqueousammbniwsolution; ThsSOllidned' coppercom'plex'dlssolvesm'wa' tion is Sting-d for 5110mm at: 80-40? Cd heatedter withavivid bluecolor and inconcentrated sulwithin 1 hour. to-boilinganda boiled for 15: hours furic 'aCidJWith b s r l dm t is under; refluxT w, complex; cgppep coma dyed in vivid greenishblueshades. of very goodpound thus obtained-is salted out; filtered and Water,washingandili'ghtefastnessa i m p e I are: rzli-ssol ved11: 200(Yparts1-of,-water with addi; tion: of 20: artsof' sodium carbonate andrwo.123.3.--parts of the sodmmsaltofthe trisazodyeparts of, pygidine; T-tmsr solutmnv there a e stuff of the; formula I l q V H038 on 11 0 o aredissolved in200& parts of water with addition added by portions at atemperature of 80-90 C. of 20 parts of sodium carbonate. To this soluandwhile stirring 500 parts of an aqueous solution there are added, byportions, and while stirtion containing 50 parts of crystallised copperring at 8090 C., 500 parts of an aqueous solu- 20 sulfate and 85 partsof a concentrated aqueous tion containing 50 parts. of, crystallisedcopper. ammoniasolution. Thev solution is stirred for 5 sulfatefa'nd' 85parts of a conoentrateel aqueous hours at 80-9U (3., heated within 1hour to ammonia solution. The mixture is stirredfor 5' boiling andboiled for hours under reflux. hours at 80-90 C., heated within 1 hourto boiling The new complex copper. compound, thus 010- and boiled for 15hours under reflux. The comtained is saltedout, filteredand dried- Itissoluplex copper compound thus obtained is salted out, blein water witha reddish, blue coloration and filtered and dried. It is soluble inwater with a in concentrated sulfuric acid with a bluish green bluecoloration and in concentrated sulphuric. coloration and dyes cotton andregenerated 681111 acid with a bluish green coloration and-dyes cotlosein navy-blue shades, possessing very good ton and regenerated cellulosein blue shades, posfastness to light, to washing and to water. sessingvery good fastness to light, to washing Example 7 and to water.

Example 5 120 parts of the sodium salt of the trisazo By replacingthestarting dyestuffi ofi'Exa-mpleelz dyestufi of formula QH' Hi6EIYCHa. HQ

SO sH H0 i 'NH:

SOsH

I SO 5H by the same quantity of the dyestufi of the for-' are dissolvedin 2000 parts of water" with addimula tion of 20 parts of sodiumcarbonate and 100 parts H038 OH 11 0? 00113 H0 and otherwise proceedingin the manner described of diethanolamine. To this solution there are inthe said. example, a, dyestufi of similar fastness added by portions andwhile stirring at -90 0., properties is obtained. 500 parts of anaqueous solution containing 50 parts of crystallised copper sulfate vandparts Examplefi of a concentrated aqueous ammonia solution.

102 parts of the sodium salt of the tri'sazo dye- The mixture isstirred. for 5 hours, at 80%9'0? stuff of the formula heated within 1hour to boiling and boiled'for H038 on moo 3on3 m 15 hours under reflux.The complex copper 750 parts of water are dropwise added thereto,compound thus obtained is salted out, filtered and the whole is filteredand the dyestufi dried. The dried. It is soluble in water with areddish-blue new copper complex dissolves in water with a coloration andin concentrated sulfuric acid with reddish-blue coloration and inconcentrated sula bluish green coloration and dyes cotton and furic acidwith a bluish green color and dyes regenerated cellulose in navy-blueshades, poscotton in navy blue shades of very good washing, sessing verygood fastness to light, to washing Water and-light fastness. and towater. What I claim is:

Example 8 1. The copper complex compound of a trisazo dyestufl whichcorresponds in its copper-free By replacing the starting dyestufl ofExample 7 t t t th formula,

. Hi0? 0cm OH if I N-BlYl by the equivalent quantity of the dyestufr ofin which A stands for the radical of a compound the formula of thenapthalene series having a hydroxy group OH HaCO OCH; OH

and otherwise proceeding in the same manner as in ortho position to theam bridge, R stands for described in the said example, a dyestufi ofsimia member selected from the group consisting of lar fastnessproperties is obtained. hydrogen, lower 'alkyl and a mononuclear radicalof the benzene series, aryl stands for a rad- Emmpze 9 ical selectedfrom the group consisting of the 99.5 parts of the sodium salt of thetrisazo dyebenzene and naphthalene series and wherein n stufi of theformula is one of the integers one to three.

0H 0H moo OCH: HO

HOaS- SOBH H0 8 NH7 are added at a temperature of 80-90 C. and under 2.The copper complex compound of the trisazo vigorous stirring to the meltof 100 parts of water, dyestufl which corresponds in its copper-free 350parts of crystalline sodium acetate and state to the formula H300 OCH:

OH OH H038 --SO;H H038 NH2 parts of crystalline copper sulfate. The meltis 3. The copper complex compound of the trisstirred for 4 hours at 90C., brought to boiling azo dyestufi which corresponds in its copper-freewithin 2 hours and boiled for further 10 hours state to the formula H0 3OH OCH: OH

a C (i) H0; soln Ho,s NH,

under reflux. The melt is cooled down to 6.. 4. The copper complexcompound of the trisazo dyestuff which corresponds in its copper-freestate to the formula mo 0 0 CH3 H 5. The copper complex compound of thetrisazo dyestufi which corresponds in its copper-free state to theformula 0 H H36 0 0 0 H3 0 H HN -S 0 311 H0 38- NH:

6 O S 0 aH 6. The copper complex compound of the trisazo dyestufl whichcorresponds in its copper-free state to the formula on on moo OCH; 0H

=N N=N HO; 301E H0 8 N H:

References Cited in the file of this patent UNITED STATES PATENTS WALTERWEHRLI.

Number Name Date 2,370,500 Sparks Feb. 27, 1945 2,390,480 West Dec. 4,1945 FOREIGN PATENTS Number Country Date ,703 G eat r tain--v---.----v--r---- Of 97

1. THE COPPER COMPLEX COMPOUND OF A TRISAZO DYESTUFF WHICH CORRESPONDSIN ITS COPPER-FREE STATE TO THE FORMULA